Pseudo-cyclocitralidene acetone and process of making same.



'NITED STATES Patented February 14, 1905.

GEORG MERLING, OF FRANKFORT-ON-THE-MAIN, AND ROBERT WELDE, OFHOOHST-ON-THE-WIAIN, GERMANY, ASSIGNORS TO FARBWERKE, VORM. MEISTER,LUOIUS & BRUN-ING, OF HOOHST-ON-THE-MAIN, GERMANY, A

CORPORATION OF GERMANY.

PSEUDO-CYCLOCITRALIDENE ACETONE AND PROCESS OF MAKING SAME.

SPECIFICATION forming part of Letters Patent No. 782,679, dated February14, 1905.

Application filed June 6, 1904. Serial No. 211,403. (Specimens) T0 atwhom it may concern.-

Be it known that we, GEORG MERLING, professor of chemistry, residing atFrankfort-onthe-Main, and ROBERT WV ELDE, chemist, residing atHochst-on-the-Main, Germany, citizens of the Empire of Germany, haveinvented cer-- tain new and useful Improvements in the Manufacture ofPerfumes, of which the following is a specification.

By condensing the ester of isopropylidenealkyl acetoacetate with sodiumalkyl acetoacetat-e followed by reduction, elimination of water, andhydrolysis trimethyl-cyclohexenecarboxylic acid or a mixture of suchacids is obtained, melting at 140 to 142 Centigrade under fifteenmillimeters pressure. The process is described in United States PatentNo. 743,305 and application, Serial No. 151,390, filed April 6, 1903.From this trimethyl-cyclohexenecarboxylic acid or the mixture containedin this acid an aldehyde or mixture of the corresponding aldehydes isobtained by distilling at moderate pressurefor instance, the calciumsalt of the acid with the equimolecular proportion of formate ofcalcium. This aldehyde or mixture of aldehydes,which we callpseudo-cyclocitral, owing to its close relationship to cyclocitral, is ayellowish oil of the consistency of cyclocitral and having in the coldan odor of carvone and in the heat a stinging smell and boiling at 76centigrade under twelve millimeters pressure. l/Ve have found that thispseudo-cyclocitral when condensed with acetone yields an unsaturatedketone or a mixture of ketones, boiling at 126 to 128 centigrade undertwelve millimeters pressure, and which when. not diluted has an odor ofcedar and when dilutedby weight, of alcohol being added, and the wholeis allowed to stand for two hours in icewater and then for several hoursat ordinary temperature. The brownish solution is then diluted withwater, neutralized or acidified with an acid, preferably tartaric acid,and distilled with steam. After the excess of acetone is expelleduncondensed pseudo-cyclocitral and pseudo-cyclocitralideneacetone passover with the steam as colorless oil, which is separated from thedistillate by shaking it with ether. The ethereal solution is dried withdehydrated sodium sulfate, and the oil remaining after distilling theether is separated by fractional distillation in a vacuum intopseudo-cyclocitral and pseudo-cyclocitralideneacetone.

Pseudo-cyclocitralideneacetone is also obtained if pseudo-cyclocitral isheated with acetone to a high temperature in a closed tube in theabsence of condensing agents. Pseudocyclocitral condenses in a similarmanner also with other ketones and their derivatives.

Thus an oily condensation product is obtained if under the sameconditions as with acetone pseudo-cyclocitral is condensed withethyl-methylketone. It boils at 138 to 135 centigrade under eightmillimeters pressure. It was not to be foreseen thatpseudo-cyclocitralideneacetone and its homologues are valuable perfumes,the more so as we have shown that the hydrogenized cyclic aldehydes,among which also those chemically related to pseudocyclocitral obtainedaccording to United States Patent No. 714,931 and German Pat- .ent No.142,139, generally do not yield perfumes when condensed with acetone.

Having now described our invention, what orless oils, soluble inalcohol, ether, benzene and ligroin and having the odor of violets andtea-roses.

3. As a new product the pseudo-cyclocitralideneacetone, being acolorless oil, soluble in alcohol, ether, benzene and ligroin, boilingat 133 to 135 centigrade under eight millimeters pressure and having theodor of violets.

In testimony that We claim the foregoing as our invention We have signedour names in 10 presence of two subscribing Witnesses.

GEORG MERLING. ROBERT VVELDE. Witnesses:

ALFRED BRIsBoIs, JOSEPH FLACH.

